Weygand/Hilgetag Preparative Organic Chemistry

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68 Formation of carbon-hydrogen bonds the aromatic series; but the method fails with imidoyl chlorides of aliphatic carboxylic acids. By a similar process, von Braun and Rudolph 459 obtained
Replacement of oxygen by hydrogen 69 small amounts of hydrogen iodide are sometimes added. For example, oethylbenzoic acid is best prepared from #-methylphthalide by the following modification of Giebe's directions: 463 Glacial acetic acid (390 ml), red phosphorus (24 g), and iodine (8 g) are placed in a roundbottomed flask (11) and set aside for 20 mm, whereupon reaction between the phosphorus and the iodine sets in slightly exotherjnally. Water (8 ml), constant-boiling hydriodic acid (2 ml), and a-methylphthalide (100 g) are then added and the whole is boiled under reflux for 160 h. The mixture is then filtered whilst hot from the phosphorus and poured, with stirring, into a solution of sodium hydrogen sulfite (35 g) in water (1.5 1); the brown color of the iodine disappears and 0-ethylbenzoic acid separates as colorless crystals. After cooling, the mixture is filtered and the filtrate is concentrated, whereby a further small amount of 0-ethylbenzoic acid is obtained (total, 80 g). A little (10 g) of the methylphthalide is recovered by ether-extraction of the concentrated filtrate, and the yield of acid calculated on phthalide consumed amounts to 90%. For purification, oethylbenzoic acid is recrystallized from water, being thus obtained completely colorless. Hydroxy carboxylic acids are also reduced similarly to carboxylic acids. For instance, diphenylacetic acid is obtained in more than 90% yield from benzilic acid. 464 Direct replacement of hydroxyl groups by hydrogen can be effected equally by combination of a non-noble metal with an acid or alcohol and by catalytic hydrogenation. The reaction is favored by neighboring unsaturated linkages, aromatic systems, or carbonyl groups, and is often only possible when such are present. An example—admittedly not one that is preparatively important— is the reaction cinnamyl alcohol with sodium and alcohol as described by Klages: 465 the product mixture contains mainly propylbenzene with a little propenylbenzene C6H5—CH^CH—CH3. The propylbenzene could not have been formed from 3-phenyl-l-propanol C6H5CH2CH2CH2OH since the latter is completely unchanged in the reaction conditions. 4-Isopropylbenzyl alcohol (CH3)2CH—C6H4—CH2OH, containing the aromatic system next to the alcoholic hydroxyl group, gives cymene when boiled for a long time even with zinc dust alone. And the alcoholic group of hydroxy ketones esterified by acetic acid are boiled for several hours with zinc dust in glacial acetic acid the acetoxy group is replaced directly by hydrogen, the neighboring keto group remaining unaffected. 467 A tertiary hydroxyl group is replaced appreciably more easily than a secondary or primary one. For instance, linalool (CH3)2C^CHCH2CH2C(CH3) • (OH)—CH=CH2, whose tertiary hydroxyl group lies next to a double bond, is converted into the hydrocarbon diene even by zinc dust in a bomb tube. 468 In fact, it is often possible to decide from the occurrence or non-occurrence of this reaction whether a hydroxyl group is tertiary as opposed to secondary or primary. 469 Naturally the reduction is more usually effected by combinations of zinc dust with hydrochloric acid, acetic acid, or sodium hydroxide solution. For 463 G. Giebe, Ber. Deut. Chem. Ges., 29, 2533 (1896). 464 C. S. Marvel, F. D. Hager, and C. E. Candle, Org. Syn., Coll. Vol. I, 224 (1947). 465 A. Klages, Ber. Deut. Chem. Ges., 39, 2587 (1906). 466 H. Stobbe, Ber. Deut. Chem. Ges., 35, 911 (1902). 467 R. S. Rosenfeld and T. F. Gallagher, /. Amer. Chem. Soc, 11, 4367 (1955). 468 F. W. Semmler, Ber. Deut. Chem. Ges., 27, 2520 (1894). 469 F. W. Semmler, Ber. Deut. Chem. Ges., 33, 776 (1900).
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PREPARATIVE ORGANIC CHEMISTRY
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WEYGAND/HILGETAG PREPARATIVE ORGANI
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Foreword to the 4 th Edition The fi
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Summary of Contents Introduction: O
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X Contents II. Addition of hydrogen
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x ii Contents II. Replacement of ha
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xiv Contents II. Esters 368 1. Repl
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xvi Contents 1. Replacement of nitr
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xviii Contents 5. Cleavage of the S
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xx Contents Chapter 11. Formation o
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xxii Contents 1.3. Formation of new
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xxiv Contents IV. Rearrangement of
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Introduction: Organization of the M
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PART A Reactions on the Intact Carb
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6 Formation of carbon-hydrogen bond
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8 Formation of carbon-hydrogen bond
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10 Formation of carbon-hydrogen bon
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118 Formation of carbon-halogen bon
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240 Formation of c arbon-halogen bo
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274 Formation of carbon-oxygen bond
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392 Cleavage of carbon-oxygen bonds
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CHAPTER 6 Formation of Carbon-Nitro
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406 Formation of carbon-nitrogen bo
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48 8 Formation of carbon-nitrogen b
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550 Alteration of nitrogen groups i
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CHAPTER 8 Formation of Carbon-Sulfu
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602 Formation of carbon-sulfur bond
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694 Formation of carbon-phosphorus
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CHAPTER 10 Formation of Metal-Carbo
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750 Formation of metal-carbon bonds
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7 52 Formation of metal-carbon bond
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814 Formation of carbon-carbon mult
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PARTB Formation of new carbon-carbo
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Addition to C=C bonds 847 Under the
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Addition to C= C bonds 849 A radica
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Addition to C=C bonds 851 ful catal
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formation (b) that is necessary for
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Addition to C —C bonds 855 Nitril
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Addition to C —C bonds 857 3,6-ep
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Addition to C—C bonds 8 59 Stereo
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Addition to C=C bonds 861 6. Additi
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Addition to C=C bonds 863 In this c
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Addition to C=C bonds 865 are added
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Addition to C=C bonds 867 amount of
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Addition to the C=O bond 869 Such a
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Addition to the C=O bond 871 Such c
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Addition to the C=O bond 873 3. For
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Addition to the C=O bond 875 In hyd
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Addition to the C=O bond 877 Finely
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Addition to the C=O bond 879 the te
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Addition to the C=O bond 881 A Grig
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Addition to the C=O bond 883 c. Tre
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Addition to the C= O bond 885 The d
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Addition to C-N multiple bonds 887
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C-C linkage by removal of hydrogen
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C~C linkage by removal of hydrogen
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C-C linkage by replacement of halog
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esters: 634 ' 640 ' 641 C-C linkage
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C-C linkage by replacement of hydro
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C-C linkage by replacement of OR by
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C-C linkage by replacement of O-acy
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C-C linkage by replacement of nitro
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tions (see also page 957): C-C link
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Removal of halogen with formation o
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Formation of a new C=C bond by remo
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Removal of sulfur with formation of
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Removal of phosphorus with formatio
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PART C Cleavage of Carbon-Carbon Bo
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Removal of carbon dioxide 1005 Only
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Removal of carbon dioxide 1007 resp
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Removal of carbon dioxide 1009 e. N
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Removal of carbon dioxide 1011 Hydr
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Removal of carbon d ioxide 1013 Thi
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Removal of carbon d ioxide 1015 as
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Removal of carbon dioxide 1017 char
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Removal of carbon dioxide 1019 Conv
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Removal of carbon monoxide 1021 Thi
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Removal of carbon monoxide 1023 lab
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Removal of carbon monoxide 1025 It
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Removal of other fragments 1027 1.
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Removal of other fragments 1029 sol
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Removal of other fragments 1031 The
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Oxidative cleavage of C-C bonds in
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Oxidative degradation of olefins 10
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Oxidative cleavage of carbon-carbon
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Hydrolytic cleavage 1047 Cleavage b
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PART D Rearrangements of Carbon Com
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Migration of a multiple bond 1055 i
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Migration of a multiple bond 1057 A
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2 hours at 250-270°, thus: 54 Rear
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Rearrangement of halogen compounds
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Migration from oxygen to carbon 106
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Migration from nitrogen to carbon 1
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Wagner-Meerwein rearrangement and r
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Cope rearrangement; valence isomeri
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Cope rearrangement; valence isomeri
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Rearrangement on decomposition of d
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Rearrangement on decomposition of d
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Appendix I Purification and drying
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Purification and drying of organic
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Preparation and purification of gas
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Preparation and purification of gas
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Preparative organic work with small
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SUBJECT INDEX This index deals prim
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Acetophenone, co-amino-, 451 —, b
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Aldehyde nitrates, 423 Aldehydes, a
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Amidic acids, 485 Amidines, 472 —
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Aporphine, 970 D-Arabinose, 1029
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Benzene, pentaphenyl-, 831 — ,pen
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Butane, l-bromo-4-chloro-, 238 —,
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Propane, l,2,3-trichloro-2-methyl-,
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Sulfoxides, 630, 667, 668 —, redu
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Thiouronium salts, 692 , S-cyclohex
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Valence isomerization, 1088 Valeral
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